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Definitions

• the present disclosure relates generally to methods and active materials for purifying gas streams containing halide as a contaminant, for example, in amounts as low as parts-per-million (ppm) or even parts-per-billion (ppb).
• Halogen products and byproducts present a serious problem in the chemical industry by causing, among other things, deactivation of downstream catalysts and corrosion of equipment.
• halide such as hydrogen chloride can significantly reduce process efficiency by poisoning a variety of catalysts such as reformer catalysts, high- temperature shift catalysts, Fischer-Tropsch catalysts and, in particular, copper- based low-temperature shift catalysts.
• catalysts such as reformer catalysts, high- temperature shift catalysts, Fischer-Tropsch catalysts and, in particular, copper- based low-temperature shift catalysts.
• less than 1 ppm halide can severely deactivate downstream catalysts in ammonia and hydrogen plants, especially copper-based catalysts.
• the present invention addresses the need for a sensitive purification method of a gas stream containing relatively low amounts of halide.
• the disclosure provides for a purification of the gas stream containing halide in amounts as low as parts-per-million (ppm) or even as low as parts-per-billion (ppb).
• the disclosure provides a method for reducing halide concentration in a gas stream, the method comprising contacting the gas stream with an active material under a set of process conditions, the active material comprising:
• the one or more first metals being selected from the group consisting of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold; and
• the one or more second metals being selected from the group consisting of alkali metals, alkaline earth metals, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, and rhenium.
• the disclosure provides an active material useful in the methods of the disclosure.
• active material comprises:
• one or more second metals being selected from the group consisting of alkali metals, alkaline earth metals, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, and rhenium.
• the one or more first metals are each present in a metallic state; and the one or more second metals are each present in a metal oxide and/or metal hydroxide state.
• Ranges can be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
• contacting includes the physical contact of at least one substance to another substance.
• halide includes substance containing fluoride, chloride, bromide, or iodide.
• the halide of interest can be, e.g., hydrogen halide, ammonium halide or an organic halide, or a combination thereof.
• the halide of interest is hydrogen halide, e.g., hydrogen chloride.
• the halide of interest is an organic halide, such as an alkyl halide (e.g., alkyl chloride).
• the term "sufficient amount” and “sufficient time” includes an amount and time needed to achieve the desired result or results, e.g., dissolve a portion of the polymer.
• weight percent is based on the total weight of the formulation or composition in which the component is included (e.g., on the total amount of the active material).
• the methods and active materials described herein can be configured by the person of ordinary skill in the art to meet the desired need.
• the disclosed methods, materials and apparati provide several unmet advantages to the purification of gas streams.
• the methods described herein can be used to significantly reduce the concentration of halide in the gas stream, and in some embodiments can be used to substantially remove all halide from the gas stream.
• the method reduces the concentration of halide present in amounts as low as parts-per-million (ppm) or even as low as parts-per-billion (ppb).
• the methods, materials and apparati can be adapted for use with gas streams regardless of whether they contain steam.
• One embodiment of the invention is an active material including:
• one or more first metals being selected from the group consisting of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold;
• metals alkaline earth metals, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, and rhenium.
• the one or more first metals and the one or more second metals can be in any oxidation state at atmospheric conditions; as described below, they can be selected to be in certain particular oxidation states at a set of desired process conditions.
• Another embodiment of the invention is a method for reducing the concentration of halide from a gas stream that includes contacting the gas stream with an active material as described herein under a set of process conditions, under which process conditions the one or more first metals are each present in a metallic state, and the one or more second metals are each present in a metal oxide and/or metal hydroxide state.
• the one or more first metals are each present in a metallic state under the process conditions. That is, under the process conditions (e.g., temperature, pressure, oxygen content, water content, hydrogen content, hydrocarbon content, carbon monoxide content, carbon dioxide content, and the like) the one or more first metals are substantially in a fully reduced oxidation state.
• At least about 80%, at least about 90%, at least about 95%, or even at least about 99% of the atoms of the one or more first metals are in a fully reduced oxidation state.
• the one or more first metals can be present, for example, as one or more discrete substantially metallic phases in the active material.
• the one or more second metals are each present in a metal oxide and/or hydroxide state under the process conditions. That is, under the process conditions (e.g., temperature, pressure, oxygen content, water content, hydrogen content, hydrocarbon content, carbon monoxide content, carbon dioxide content, and the like) the one or more second metals are substantially in an oxidized oxidation state, bound to oxygen atoms in the form of an oxide or hydroxide material. For example, in certain embodiments, at least about 80%, at least about 90%, at least about 95%, or even at least about 99% of the atoms of the one or more second metals are in an oxidized oxidation state.
• the one or more second metals can be present, for example, as one or more discrete substantially oxide and/or hydroxide phases in the active material.
• the active materials disclosed herein include a metallic species in a metallic state and a metallic species in an oxide and/or hydroxide state.
• gas phase halide adsorbs and breaks down to halogen atoms (e.g., chlorine atoms) on the metallic surface.
• halogen atoms e.g., chlorine atoms
• the halogen atoms migrate to the metal oxide and/or hydroxide surface to be trapped as metal halides.
• the disclosed methods and active materials may be utilized for purifying gas streams having a wide variety of halides.
• the halide in the gas stream is hydrogen chloride.
• these methods and active materials may also be utilized for purifying gas streams having a wide variety of halide levels.
• the gas stream contains from about 0.001 to about 1000 ppm halide.
• the gas stream contains about 0.01 to about 0.1 ppm, or about 0.01 to about 1 00 ppm, or about 0.001 ppm to about 10 ppm, or about 0.01 to about 10 ppm, or about 0.1 to about 0.5 ppm, or about 0.1 to about 1 ppm, or about 0.1 to about 10 ppm, or about 1 to about 100 ppm of halide. In other embodiments, the gas stream contains about 0.3 to about 0.4 ppm of halide.
• the disclosed methods and active materials can also be effective in removing other contaminants from a gas stream.
• the disclosed methods and active materials can additionally remove one or more sulfur-containing compounds (e.g., COS, H 2 S) from the gas stream.
• the disclosed methods and active materials can also remove the sulfur-containing compounds from the gas stream that does not contain a halide.
• the disclosed methods and active materials can additionally remove metal dust from the gas stream.
• the gas stream may not contain a halide.
• One embodiment of the disclosure provides for a method or an active material as described herein, where the one or more first metals are selected from the group consisting of iron, cobalt, nickel, copper, palladium, and silver.
• the one or more first metals are copper, silver, or gold.
• the one or more first metals are copper or silver.
• the one or more second metals are selected from the group consisting of alkali metals (e.g., Li, Na, K or Rb; or Li, Na or K), alkaline earth metals (e.g., Be, Mg, Ca, Sr or Ba; or Mg, Ca, Sr or Ba), vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, and rhenium.
• alkali metals e.g., Li, Na, K or Rb; or Li, Na or K
• alkaline earth metals e.g., Be, Mg, Ca, Sr or Ba; or Mg, Ca, Sr or Ba
• vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, and rhenium e.g., Li, Na, K or Rb; or Li, Na or K
• the one or more second metals are selected from of alkali metals (e.g., Li, Na, K or Rb; or Li, Na or K) and alkaline earth metals (e.g., Be, Mg, Ca, Sr or Ba; or Mg, Ca, Sr or Ba).
• alkali metals e.g., Li, Na, K or Rb; or Li, Na or K
• alkaline earth metals e.g., Be, Mg, Ca, Sr or Ba; or Mg, Ca, Sr or Ba.
• the one or more second metals are rubidium, cesium, strontium, or barium.
• the one or more second metals are cesium or barium.
• the one or more second metals are vanadium, niobium, chromium, molybdenum, manganese, or technetium.
• the one or more second metals are vanadium, chromium, or manganese.
• the ratio of the metal present in the metallic state to the metal present in the metal oxide and/or metal hydroxide state can be important for the performance of the active material.
• the ratio (i.e., by weight, calculated as oxides) of the one or more first metals to the one or more second metals is in the range of about 1 :7 to about 7:1 .
• the ratio of the one or more first metals to the one or more second metals is in the range of about 1 :5 to about 5:1 , or about 1 :4 to about 4:1 , or about 1 :3 to about 3:1 , or about 1 :2 to about 2:1 , or about 1 :1 , or about 1 :2, or about 1 :3, or about 1 :4, or about 1 :5, or about 1 :6, or about 1 :7, or about 2:1 , or about 3:1 , or about 4:1 , or about 5:1 , or about 6:1 , or about 7:1 .
• the ratio of the one or more first metals to the one or more second metals is in the range of about 1 :4 to about 4:1 .
• the ratio of the one or more first metals to the one or more second metals is in the range of about 1 :2 to about 2:1 .
• the amount of the one or more first metals and one or more second metals can be important for the performance of the active material.
• the total weight of the one or more first metals and the one or more second metals is about 5 to about 1 00 weight % of the active material.
• the total weight of the one or more first metals and the one or more second metals is about 5 to about 95 weight %, or about 5 to about 90 weight %, or about 10 to about 100 weight %, or about 10 to about 95 weight %, or about 10 to about 90 weight %, or about 15 to about 100 weight %, or about 15 to about 95 weight %, or about 15 to about 90 weight %, or about 20 to about 1 00 weight %, or about 20 to about 95 weight %, or about 20 to about 90 weight %, or about 30 to about 1 00 weight %, or about 30 to about 95 weight %, or about 30 to about 90 weight %, or about 30 to about 80 weight %, or about 30 to about 70 weight %, or about 30 to about 60 weight %, or about 30 to about 50 weight %, or about 50 to about 70 weight %, or about 50 to about 80 weight %, or about 50 to about 90 weight %, or about 30 to about 1
• the total weight of the one or more first metals and the one or more second metals is about 30 to about 90 weight % of the active material.
• the active materials may include other ingredients, such as those conventional in the art.
• the active material may further comprise one of more carriers or binders, as would be apparent to the person of ordinary skill in the art.
• the active material further comprises a carrier or binder selected from the group consisting of zinc oxide, aluminum oxide, silicon dioxide, titanium oxide, a clay, a zeolite, carbon, a cement, or a combination thereof.
• the carrier or binder can be selected from the group consisting of zinc oxide, aluminum oxide, silicon dioxide, titanium oxide, magnesium oxide (e.g., when magnesium is not a second metal), manganese oxide (e.g., when manganese is not a second metal), zirconium oxide (e.g., when zirconium is not a second metal), a clay, a zeolite, carbon, a cement, or a combination thereof.
• zinc oxide aluminum oxide
• silicon dioxide titanium oxide
• magnesium oxide e.g., when magnesium is not a second metal
• manganese oxide e.g., when manganese is not a second metal
• zirconium oxide e.g., when zirconium is not a second metal
• a clay e.g., when zirconium is not a second metal
• the carrier or binder is aluminum oxide. In another embodiment, the carrier or binder is silicon dioxide. In another embodiment, the carrier or binder is zinc oxide.
• the carriers or binders can be provided in a total amount, for example, in the range of from about 0.5 to about 95 weight % of the total weight of the active material.
• the one or more carriers or binders are provided in a total amount, for example, in the range of about 0.5 to about 80 weight %, or about 0.5 to about 30 weight %, or about 10 to about 95 weight %, or about 5 to about 70 weight %, or about 10 to about 70 weight %, or about 5 to about 60 weight %, or about 10 to about 60 weight %, or about 5 to about 50 weight %, or about 1 0 to about 50 weight %, or about 1 to about 50 weight %, or about 15 to about 50 weight %, or about 25 to about 50 weight % of the total weight of the active material.
• the active material can be used in unsupported form, for example, when combination of the one or more first metals and the one or more second metals provides the desired physical properties to the active material.
• one or more of the first metals and/or second metals can themselves act as a carrier or binder for the other components.
• the active material may be provided in any suitable form.
• the active material can be formed as spheres, pellets, cylinders (hollow or otherwise), symmetrical or asymmetrical tri-quadrulobes, or other shape/medium, for example, using extrusion methods.
• the active material may have any suitable pore volume such as about 0.1 to about 1 .5 cm 3 /g, or about 0.5 to about 1 .5 cm 3 /g, about 1 to about 1 .5 cm 3 /g, or about 0.1 to about 1 cm 3 /g, or about 0.1 to about 0.5 cm 3 /g, or about 0.1 cm 3 /g, or about 0.5 cm 3 /g, or about 1 cm 3 /g, or about 1 .5 cm 3 /g.
• the active material has a pore volume of about 0.2 to about 1 .2 cm 3 /g.
• the active material has a pore volume of about 0.3 to about 0.9 cm 3 /g.
• the surface area of the active material may be from about 1 0 to about 400 m 2 /g.
• Other suitable surface areas may be from about 1 0 to about 400 m 2 /g, or about 50 to about 400 m 2 /g, or about 100 to about 400 m 2 /g, or about 200 to about 400 m 2 /g, or about 300 to about 400 m 2 /g, or about 10 to about 300 m 2 /g, or about 50 to about 300 m 2 /g, or about 100 to about 300 m 2 /g, or about 200 to about 300 m 2 /g, or about 10 to about 200 m 2 /g, or about 50 to about 200 m 2 /g, or about 1 00 to about 200 m 2 /g.
• the active material has a surface area of about 20 to about 300 m 2 /g.
• the active material has a surface area of about 30 to about 200 m 2 /g.
• the active material may be prepared by conventional procedures, as would be understood by the person of ordinary skill in the art.
• the active material is made by precipitation.
• the active material is made by precipitation of one or more water soluble raw materials with a precipitation agent.
• Each raw material may be a water soluble metal material such as, but not limited to, a metal nitrate, a metal sulfate, a metal halide, or a metal acetate; certain raw materials may be provided with the metal species in the anion (e.g. molybdate, manganate, chromate, tungstate, vanadate).
• the raw material is copper nitrate, manganese nitrate, or copper ammine.
• the precipitation agent may be, for example, ammonium hydroxide, ammonium carbonate, a metal hydroxide, or a metal carbonate.
• the precipitation agent is Na 2 CO 3 .
• the person of ordinary skill in the art can select other suitable precipitation agents.
• the person of ordinary skill in the art will also appreciate that such materials can be formed with or without a binder, depending on the particular metals used and the desired active material properties.
• the active material is made by wetting a carrier material (or a material comprising one or more of the first and/or second metals) with one or more raw materials.
• Each raw material may be a water soluble metal material such as, but not limited to, a metal nitrate, a metal sulfate, a metal halide, metal amine, or a metal acetate; certain raw materials may be provided with the metal species in the anion (e.g. molybdate, manganate, chromate, tungstate, vanadate).
• the raw material is copper nitrate, manganese nitrate, silver nitrate, or ammonium molybdate.
• the precipitated or impregnated material can be dried to provide the active material.
• the precipitated or impregnated material is also calcined. Calcining can be performed at any appropriate stage, e.g., before or after formation of the active material into a desired shape.
• the methods and active materials described herein can be used to reduce halide concentration in gas streams in a wide variety of processes.
• the methods and active materials can be used in advance of processes such as reforming, high temperature shift, Fischer-Tropsch catalysis, and, in particular, of the copper-based low temperature shift to protect poisoning of downstream catalysts.
• the processes and active materials described herein can be used under a wide variety of process conditions (e.g., temperature, pressure, oxygen content, water content).
• process conditions include a process pressure in the range of about 100 kPa to about 10 MPa.
• the process conditions include a pressure of about 1 20 kPa to about 5 MPa.
• the process conditions include a pressure of about 120 kPa.
• the process conditions include a process temperature in the range of about 100 to about 500 °C.
• Other suitable temperatures include, but are not limited to a range of about 100 to about 300 °C, or about 150 to about 250 °C, or about 150 to about 200 °C, or about 200 to about 300 °C, or about 200 to about 250 °C, or about 100, or about 150 °C, or about 200, or about 250 °C, or about 300 °C.
• the reference carrier material was extruded alumina (CS-1 ), prepared with pore volume (PV) of 0.71 cm 3 /g and surface area (SA) of 200 m 2 /g.
• An active material was prepared as described generally in Comparative Example 2, using 50% Mn(N0 3 )2 solution instead of the Cu(N0 3 )2 solution. This active material had 20.7 % Mn0 2 on the extrusion (CS-3).
• An active material was prepared as described generally in Comparative Example 2, using 15.5% AgN0 3 solution instead of the Cu(N0 3 ) 2 solution. This active material had 1 1 .8 % AgO on the extrusion (CS-4).
• An active material was prepared as described generally in Comparative Example 2, using 15.5 wt% of Mo as ammonium molybdate solution instead of the Cu(N0 3 ) 2 solution. This active material had 16.7 % Mo0 3 on the extrusion (CS-5).
• Example 2 An active material was prepared as described generally in Example 2, using 100 cm 3 Cu(N0 3 ) 2 and Mn(N0 3 ) 2 solution with 3 wt% of Cu + 12 wt% of Mn as metals. This active material had 8.0 % CuO and 24.8 % Mn0 2 on the extrusion (S-1 ).
• S-1 extrusion
• An active material was prepared as described generally in Example 1 , using 60 cm 3 Cu(N0 3 )2 and Mn(N0 3 )2 solution with 5 wt% of Cu + 1 0 wt% of Mn as metals. This active material had 10.6 % CuO and 16.3 % Mn0 2 on the extrusion (S-
• An active material was prepared as described generally in Example 1 , using 50 cm 3 Cu(N0 3 )2 and Mn(N0 3 )2 solution with 8 wt% of Cu + 8 wt% of Mn as metals. This active material had 13.1 % CuO and 12.2 % Mn0 2 on the extrusion (S-
• An active material was prepared as described generally in Example 1 , using 60 cm 3 Cu(N0 3 ) 2 and Mn(N0 3 ) 2 solution with 10 % Cu + 5 % Mn as metals. This material had 17.2% CuO and 8.1 % Mn0 2 on the extrusion (S-4).
• the material was prepared as described generally in Example 1 , with the exception of using 30 cm 3 50 % Mn(N0 3 ) 2 solution and 15.5% AgN0 3 solution. This material had 14.6 % Mn0 2 and 5.1 % AgO on the extrusion (S-5).
• the material was prepared as described generally in Example 1 , with the exception of using 30 cm 3 15.5 % Cu(N0 3 ) 2 solution and 15.5 % Mo ammonia molybdate solution. This material had 17.4 % CuO and 5.2% Mo0 3 on the extrusion (S-6).
• An active material (S-7) having 56 % CuO, 10 % Mn0 2 and 34 % Al 2 0 3 was prepared by co-precipitating Cu(N0 3 ) 2 , Mn(N0 3 ) 2 and AI(N0 3 ) 3 with Na 2 C0 3 . The precipitate was washed followed by drying and calcining. The calcined powder was formed to tablets by pressing, which had PV of 0.2 cm 3 /g and SA of 44 m 2 /g.
• a material (S-8) was prepared as described generally in Example 7, with the exception of using different concentration of Mn(N0 3 ) 2 .
• the material had 62 % CuO, 0.5 %Mn0 2 and 38 % Al 2 0 3 .
• a material (S-9) having 44 % CuO, 44 % ZnO and 1 3 % AI 2 O 3 was prepared by precipitating copper amine, zinc amine and AI(OH) 3 with Na 2 CO 3 . The precipitate was washed followed by drying and calcining. The calcined powder was formed to tablets by pressing.
• a material (S-1 0) having 57 % CuO, 30 % ZnO, 1 % Cs 2 O and 12 % AI 2 O 3 was prepared by impregnation of Cs 2 CO 3 compound on to copper/zinc/aluminum oxide, which was made by precipitation as described generally above. The powders were pressed into tablets.
• a material (S-1 1 ) having 22 % CuO, 50 % ZnO, 12 % Cr 2 O 3 and 15 % AI 2 O 3 was prepared by precipitation. The precipitate was washed, followed by drying and calcining. The calcined powder was formed into tablets by pressing, which tablets had PV of 0.28 cm 3 /g and SA of 74 m 2 /g.
• a material (S-1 2) was prepared as described generally in Example 7, with the exception of using a different solution concentration.
• the final product had 23 % CuO, 36 % ZnO and 41 % Cr 2 O 3 .
• a material (S-1 3) having 38 % CuO, 43 % ZnO, 9 % BaO and 10 % AI 2 O 3 was prepared by precipitation. The precipitate was washed followed by drying and calcining. The calcined powder was formed into tablets by pressing, which tablets had PV of 0.2 cm 3 /g and SA of 53 m 2 /g.
• a material (S-14) having 1 9 % CuO, 69 % MnO 2 , 2.5 % K 2 O, 1 .5 % AI 2 O 3 and 8 % SiO 2 was prepared by precipitation. The precipitate was washed followed by drying and calcining. The calcined powder was formed into tablets by pressing, which tablets had PV of 0.53 cm 3 /g and SA of 210 m 2 /g.
• the halogen removal test was performed at a fixed bed system with a 018mm glass reactor. 10 cm 3 of formed particles were loaded in the reactor. The active material was treated with 3 % H 2 /N 2 stream for 12 hours at 220 °C before performing the halogen removal test.
• Halogen removal test 1 was performed with 330 ppb HCI (V) in 33.5 % H 2 / 33.5 % N 2 / 33 % H 2 0 at 120 kPa and 220 °C.
• the outlet stream was condensed with a chiller. Hydrogen chloride in the condensation was analyzed periodically with ion chromatography (IC). After 127 hours on stream, the spent samples were unloaded and analyzed for picked up Chloride content. The results are summarized in the Table 1 .
• Spent S-13 127 684 [0061]
• a second halogen removal test was performed with 3 ppm HCI (V) in a simulated syngas composition for copper-based low temperature shift catalysts in 58 % H 2 / 2 % CO / 6 % CO 2 / 1 % N 2 / 33 % H 2 O at 120 kPa and 200 °C.
• the active material was treated with 3 % H 2 /N 2 stream for 12 hours at 200 °C before performing the halogen removal test.
• Table 2 The results are summarized in Table 2, and demonstrate that the active materials described herein can function at different gas compositions, and thus can be used for syngas purification before the water gas shift catalyst bed to guard against poisoning of the copper-based water gas shift catalyst.
• a third halogen removal test was performed with 3 ppm HCI (v) or 35 ppm (v) in 33.5 % H 2 / 33.5 % N 2 / 33 % H 2 O at 120 kPa and 220 °C.
• the active material was treated with 3% H 2 /N 2 stream for 12 hours at 220 °C before performing the halogen removal test.
• Table 3 The results are summarized in Table 3, and demonstrate that the active materials described herein can be used for chloride removal at higher chloride concentrations.

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